Combinations of active ingredients for inhibiting or controlling nitrification

ABSTRACT

This patent describes nitrification inhibitors characterized by the fact that they contain as their active ingredients 1-hydro-1,2,4-triazole, a substituted 1-hydro-1,2,4-triazole, or their salts or metallic complexes, plus at least one other chemical compound, such as a substituted pyrazole, or its salts or metallic complexes, dicyanodiamide, guanyl thiocarbamide, thiocarbamide, ammonium rhodanide, or ammonium thiosulfate, where said combinations exhibit readily recognizable synergetic effects compared to the case where said chemical compounds are employed alone, and thus provide benefits in terms of better efficacies, reduced dosages, and/or cost savings.

BACKGROUND OF THE INVENTION

The present invention concerns combinations of two or more activeingredients for inhibiting or controlling nitrification of ammonia inarable topsoil and subsoil.

Reduced nitrogen, such as that contained in ammonia, ammonium compounds,or nitramide, present in arable soil is rapidly transformed intonitrates via intermediate nitrite stages by bacterial action. The ratesat which nitrification proceeds are largely determined by thetemperatures, moisture contents, pH, and bacterial activities of thesoils involved. A counteracting effect here is that, unlike the nitrogenof ammonia or ammonium compounds, that of nitrates will not be sorbed bythe sorbing agents present in arable soil, and will thus eitherprecipitate out and be washed away by surface runoff, or will end upbeing deposited in deep-lying strata extending down to the water tableand below levels accessible to plants. Under adverse weather or soilconditions, runoff losses may exceed 20% of total available reducednitrogen. To be added to these losses are denitrification losses due toreduction of nitrates formed by nitrification processes to gaseouscompounds under anaerobic conditions, losses that may reach comparablelevels.

Employing suitable chemicals to inhibit or control nitrification canpromote utilization of nitrogen fertilizers by plants. Moreover, thisapproach provides further benefits in that it reduces nitrateconcentrations in ground water and surface runoff, and counteractsnitrate enrichment in cultivated plants, particularly forage crops.

In addition to substituted pyrazoles (U.S. Pat. No. 3,494,757, DD133088), other known solutions to these problems involve employingdicyanodiamide (DCD) (DE 2702284, DE 2714601), guanyl thiocarbamide (JP7301138), thiocarbamide (DE 2051935), 1,2,4-triazole,4-amino-1,2,4-triazole (JP 7104135), or other triazole derivatives (U.S.Pat. No. 3,697,244, U.S. Pat. No 3,701,645).

Combinations of active ingredients supposedly superior to theabove-mentioned compounds when employed alone have also beenrecommended. Among those combinations worth noting here are admixturesof pyrazoles and DCD (DD 222471) or guanyl thiocarbamide (DD 247894),admixtures of 4-amino-1,2,4-triazole (ATC) and DCD (SU 1137096), andamalgams of, e.g., ATC in carbamide/thiocarbamide orcarbamide/DCD-mixtures (DD 227957). Employing admixtures ofdicyanodiamide and ammonium thiosulfate has also been recommended (DE3714729).

The disadvantages of these known nitrification inhibitors are their lowefficacies, which implies that large dosages will be required,volatilities or instabilities that are too high to allow them to be ofmuch benefit in practical applications, or decomposition rates that aretoo rapid for the types of applications involved. Moreover, althoughsome of these inhibitors retard nitrification to acceptable degrees,their efficacies are severely reduced by "incompatibility reactions"with several types of fertilizers.

SUMMARY OF THE INVENTION

The object of the present invention is identifying combinations ofactive ingredients suitable for employment in mineral and organicnitrogen fertilizers that will have synergetic effects on inhibition ofnitrification, and will thus be more beneficial than either employingthe compounds involved alone, or employing any of those combinationsmentioned above.

Surprisingly, it has been found that when employed for inhibiting orcontrolling nitrification in arable topsoil and subsoil, combinations ofactive ingredients containing 1-hydro-1,2,4-triazole, a substituted1-hydro-1,2,4-triazole, or their salts or metallic complexes, plus atleast one other chemical compound, such as a substituted pyrazole, orits salts or coordination compounds, dicyanodiamide, guanylthiocarbamide, thiocarbamide, ammonium rhodanide, or ammoniumthiosulfate, exhibit marked synergetic effects, and are thus are moreeffective than any of these compounds when employed alone.

The ingredients of the combinations of the present invention may beadmixed in proportions ranging from 0.5: 99.5 to 99.5: 0.5. Wherecombinations contain more than two ingredients, mixing ratios may bearbitrarily adjusted for each ingredient involved.

The combinations of the present invention are beneficial in the sensethat they provide enhanced long-term effects, i.e., nitrification isinhibited over extended periods, and they thus contribute to providingthat nitrogen released by nitrogen fertilizers will be better utilized,and that these fertilizers will therefore be more effective, even wherelower dosages are employed. A related effect of employing suchcombinations is that cultivated plants have been observed to yield morebiomass.

PREFERRED EMBODIMENTS OF THE INVENTION

The combinations of active ingredients of the present invention may beemployed admixed with liquid or solid mineral or organic fertilizerscontaining nitramide or ammonium compounds, in which case they should beapplied in dosages ranging from 0.5 kg/ha to 20 kg/ha.

The following examples will serve to clarify the present invention, butshall not be construed as imposing any restrictions on same. Table 1lists a selection of those triazoles and their salts and metalliccomplexes employed as basic ingredients of those combinations studied,while Table 2 lists several of the other ingredients that were admixedwith said triazoles.

                  TABLE 1    ______________________________________    Symbol       Designation/Chemical Formula    ______________________________________    Tr           1-hydro-1,2,4-triazole    Tr × HCl                 1-hydro-1,2,4-triazole × HCl    HMT          1-hydroxy-methyl-1,2,4-triazole × HCl    Na--Tr       1-sodium-1,2,4-triazolate    Fe--Tr        Fe(Tr).sub.6 !Cl.sub.3    GTr          1-guanyl-1,2,4-triazole × HCl    CTS           Cu(Tr).sub.2 !SO.sub.4 × 2H.sub.2 O    MT            Mn(Tr).sub.4 !Cl.sub.2    ______________________________________

                  TABLE 2    ______________________________________    Symbol        Designation/Chemical Formula    ______________________________________    GTH           guanyl thiocarbamide    TH            thiocarbamide    AR            ammonium rhodanide    DCD           dicyanodiamide    ATS           ammonium thiosulfate    MP            3-methylpyrazole    CMP           1-carbamyl-3-methylpyrazole    GMP           1-guanyl-3-methylpyrazole × HCl    Mg--MP        Mg-3-methylpyrazolate    Zn--MP         Zn(MP).sub.2 !SO.sub.4    GZC           (GMPH).sub.2 ZnCl.sub.4    GM            Mg(GMP).sub.2 Cl.sub.2 × H.sub.2 O    ______________________________________

The results of employing such combinations in the examples presentedbelow were all obtained using the same methodology.

EXAMPLES

The combinations of the present invention, along with carbamide (urea),which served as a source of nitrogen, were admixed with a sandy loamsimilar to humus in the concentrations listed in the following tables(all concentrations stated in ppm are by weight, referred to the totalweight of soil involved), brought up to 50% of their maximummoisture-retention capacities, and then vigorously mixed. Theconcentration of elemental nitrogen employed was 10 mg/100 g of soil.Soil samples prepared in this fashion were placed in plastic bottles,the bottles sealed, incubated at 20° C., and the resultant rates ofnitrate formation and declines in ammonia concentrations monitored.

Percentage nitrification inhibitions were computed from the relation##EQU1## where

K is the nitrate concentration in soil samples that were admixed withnitrogen fertilizer, but had no active ingredients added,

A is the nitrate concentration in soil samples that were admixed withboth nitrogen fertilizer and active ingredients, and

B is the nitrate concentration in soil samples that were admixed withneither nitrogen fertilizer nor active ingredients.

Values of t₅₀, which are efficacy factors representing those timeperiods, expressed in days, that had elapsed until nitrificationinhibitions had declined to 50% of their initial levels, were determinedfrom nonlinear regressions applied to the temporal degradation data

Values of t₅₀ obtained in this fashion were subjected to Logit-Probittransforms (which linearize effect-dosage curves) in order to assess theeffects of the combinations involved based on the independence model ofGroeger, et al, Pharmazle 36 (1981), pp. 81-87!, which incorporates ageneralization of the theories of Gowing Weeds 8 (1960), pp. 379-391!and of Colby Weeds 15 (1967), pp. 20-22!, according to which the effectsof such combinations were regarded as synergetic if they were betterthan those of the ingredients involved when employed alone, or if thedosages required to yield given effect; were less than those predictedby the independence model.

Example 1 Combinations of 1-hydro-1,2,4-triazole (Tr) and dicyanodiamide(DCD)

Values of t₅₀ were computed and compared for cases where Tr alone, DCDalone, and admixtures of the two were employed, following themethodology referred to above.

                  TABLE 3a    ______________________________________    Values of t.sub.50 for Tr alone, DCD alone, and admixtures of the two.    1-Hydro-1,2,4-Triazole                 Dicyanodiamide    Concentration                 Concentration                              Tr:DCD    t.sub.50     ppm!         ppm!        Mixing Ratio                                         days!    ______________________________________    0.096                               5.5    0.227                               14.0    0.545                               30.0    0.909                               41.5    1.25                                46.0    2.0                                 50.0    3.0                                 52.3    5.0                                 57.0                 1.25                   10.0                 2.0                    14.3                 3.0                    17.6                 3.846                  19.7                 5.0                    22.0                 5.882                  23.6                 8.333                  27.3                 9.091                  28.4                 10.0                   29.6    5.0          5.0          50:50     73.8    3.0          3.0                    58.2    2.0          2.0                    57.1    1.25         1.25                   52.5    1.667        8.333        17:83     106.6    1.0          5.0                    71.5    0.667        3.333                  53.7    0.417        2.083                  37.1    0.909        9.091        9:91      111.8    0.545        5.445                  69.4    0.364        3.636                  45.5    0.227        2.273                  28.7    0.25         3.75         6:94      37.3    0.156        2.344                  23.9    0.19         3.81         5:95      32.1    0.119        2.38                   22.2    0.385        9.615        4:96      73.5    0.231        5.769                  41.5    0.154        3.846                  29.6    0.096        2.404                  21.3    0.196        9.804        2:98      48.1    0.118        5.882                  31.2    ______________________________________

                  TABLE 3b    ______________________________________    Percentage savings of active ingredients and incremental    improvements in efficacies, relative to those predicted    by the independence model (IM).          Con-    Tr:DCD          centration                    Empirically                              Efficacy       Dosage    Mixing          in Host Soil                    Determined                              Predicted by                                      Efficacy                                             Savings    Ratio  ppm!     Efficacy  the IM  Increment                                              %!    ______________________________________    50:50 10        74        82      -8     -53          6         58        72      -14    -68          4         57        61      -4     -17          2.5       52        48      4      14    17:83 10        100       64      36     --          6         71        50      21     55          4         54        39      14     42          2.5       37        29      8      31    9:91  10        100       53      47     --          6         69        40      29     69          4         45        31      14     47          2.5       29        23      6      29    6:94  4         47        37      10     36          2.5       30        28      2      12    5:95  4         40        34      6      25          2.5       28        26      2      11    4:96  10        92        52      40     --          6         52        61      9      40          4         37        33      4      21          2.5       27        25      2      11    2:98  10        60        46      14     48          6         39        36      3      17    ______________________________________

Example 2 Combinations of 1-hydro-1,2,4-triazole (Tr) and guanylthiocarbamide (GTH)

The experimental methodology and computerized data analyses employedhere were similar to those employed in the case of Example 1, above.

                  TABLE 4a    ______________________________________    Values of t.sub.50 for Tr alone, GTH alone, and admixtures of the two.    1-Hydro-1,2,4-Triazole                 Guanyl Thiocarbamide    Concentration                 Concentration Tr:GTH    t.sub.50     ppm!         ppm!         Mixing Ratio                                          days!    ______________________________________    0.096                                5.5    0.227                                14.0    0.545                                30.0    0.909                                41.5    1.25                                 46.0    2.0                                  50.0    3.0                                  52.3    5.0                                  57.0                 2.0                     1.0                 4.0                     9.3                 6.0                     18.4                 8.0                     28.0                 10.0                    37.4                 12.0                    47.2    5.0          5.0           50:50     63.4    2.5          2.5                     53.8    1.25         1.25                    40.3    0.909        9.091         9:91      81.8    0.545        5.445                   70.3    0.227        2.273                   19.2    0.385        9.615         4:96      60.5    0.231        5.769                   35.4    0.154        3.846                   25.1    0.196        9.804         2:98      49.4    0.118        5.882                   28.9    ______________________________________

                  TABLE 4b    ______________________________________    Percentage savings of active ingredients and incremental    improvements in efficacies, relative to those predicted    by the independence model (IM).          Con-    Tr:GTH          centration                    Empirically                              Efficacy       Dosage    Mixing          in Host Soil                    Determined                              Predicted by                                      Efficacy                                             Savings    Ratio  ppm!     Efficacy  the IM  Increment                                              %!    ______________________________________    50:50 10        95        95      0      -4          5         81        86      -6     -29          2.5       68        68      0      1    9:91  10        100       74      26     89          6         100       53      47     93          2.5       29        21      8      23    4:96  10        91        59      32     62          6         54        38      16     32          4         38        24      14     34    2:98  10        74        51      23     44          6         43        32      11     27    ______________________________________

Example 3 Combinations of 1-hydro-1,2,4-triazole (Tr) and thiocarbamide(TH)

The experimental methodology and computerized data analyses employedhere were similar to those employed in the case of Example 1, above.

                  TABLE 5a    ______________________________________    Values of t.sub.50 for Tr alone, TH alone, and admixtures of the two.    1-Hydro-1,2,4-Triazole                 Thiocarbamide    Concentration                 Concentration                             Tr:TH      t.sub.50     ppm!         ppm!       Mixing Ratio                                         days!    ______________________________________    0.1                                 5.8    0.25                                14.3    0.5                                 29.0    1.0                                 42.1    2.0                                 49.1    3.0                                 51.9    5.0                                 56.2                 2.0                    6.5                 4.0                    8.5                 8.0                    10.5                 10.0                   12.6                 16.0                   17.3    3.0          3.0         50:50      58.2    2.0          2.0                    54.8    0.909        9.091       9:91       49.9    0.545        5.445                  42.2    0.227        2.273                  27.1    0.385        9.615       4:96       37.1    0.154        3.846                  24.7    0.096        2.404                  14.9    0.196        9.804       2:98       26.4    0.118        5.882                  18.0    ______________________________________

                  TABLE 5b    ______________________________________    Percentage savings of active ingredients and incremental    improvements in efficacies, relative to those predicted    by the independence model (IM).          Con-    Tr:TH centration                    Empirically                              Efficacy       Dosage    Mixing          in Host Soil                    Determined                              Predicted by                                      Efficacy                                             Savings    Ratio  ppm!     Efficacy  the IM  Increment                                              %!    ______________________________________    50:50 6         87        80      7      40          4         82        72      10     42    9:91  10        75        63      12     39          6         63        49      14     41          2.5       40        28      12     42    4:96  10        55        48      8      24          4         37        26      11     40          2.5       22        18      5      25    2:98  10        40        38      1      5          6         27        27      0      2    ______________________________________

Example 4 Combinations of 1-hydro1,2,4-triazole (Tr) and ammoniumrhodanide (AR)

The experimental methodology and computerized data analyses employedhere were similar to those employed in the case of Example 1, above.

                  TABLE 6a    ______________________________________    Values of t.sub.50 for Tr alone, AR alone, and admixtures of the two.    1-Hydro-1,2,4-Triazole                 Ammonium Rhodanide                                Tr:AR    Concentration                 Concentration  Mixing   t.sub.50     ppm!         ppm!          Ratio     days!    ______________________________________    0.096                                5.5    0.227                                14.0    0.545                                30.0    0.909                                41.5    1.25                                 46.0    2.0                                  50.0    3.0                                  52.3    5.0                                  57.0                 2.0                     3.1                 4.0                     6.3                 8.0                     8.5                 10.0                    9.3                 16.0                    11.9    3.0          3.0            50:50    56.9    2.0          2.0                     52.5    1.25         1.25                    46.3    0.545        5.445          9:91     61.6    0.364        3.636                   40.8    0.227        2.273                   35.1    0.19         3.81           5:95     33.7    0.119        2.38                    25.7    0.196        9.804          2:98     29.1    0.118        5.882                   22.4    ______________________________________

                  TABLE 6b    ______________________________________    Percentage savings of active ingredients and incremental    improvements in efficacies, relative to those predicted    by the independence model (IM).          Con-    Tr:AR centration                    Empirically                              Efficacy       Dosage    Mixing          in Host Soil                    Determined                              Predicted by                                      Efficacy                                             Savings    Ratio  ppm!     Efficacy  the IM  Increment                                              %!    ______________________________________    50:50 6         57        57      0      -2          4         52        49      3      15          2.5       46        39      7      29    9:91  6         62        30      32     79          4         41        24      17     62          2.5       35        17      18     68    5:95  4         34        18      16     66          2.5       26        12      14     66    2:98  10        29        22      7      36          6         22        16      6      41    ______________________________________

Example 5 Combinations of 1-hydroxy-methyl-1,2,4-triazole×HCl(HMT) andguanyl thiocarbamide (GTH)

The experimental methodology and computerized data analyses employedhere were similar to those employed in the case of Example 1, above.

                  TABLE 7a    ______________________________________    Values of t.sub.50 for HMT alone, GTH alone, and admixtures of the two.    1-Hydroxy-Methyl-    1,2,4-Triazole × HCl                Guanyl Thiocarbamide    Concentration                Concentration HMT:GTH    t.sub.50     ppm!        ppm!         Mixing Ratio                                          days!    ______________________________________    0.25                                 14.8    0.5                                  22.9    0.75                                 29.7    1.0                                  37.4    2.0                                  44.1    5.0                                  50.0    7.5                                  57.1                1.0                      1.1                2.0                      3.4                4.0                      10.2                8.0                      29.1                10.0                     38.2    5.0         1.0           83:17      53.1    2.5         0.5                      44.2    1.25        0.25                     38.7    3.0         3.0           50:50      52.1    1.5         1.5                      43.1    1.0         5.0           17:83      56.9    0.5         2.5                      29.1    0.545       5.445         9:91       64.9    0.273       2.727                    28.3    0.286       5.714         5:95       61.7    0.143       2.857                    23.9    0.118       5.882         2:98       39.4    ______________________________________

                  TABLE 7b    ______________________________________    Percentage savings of active ingredients and incremental    improvements in efficacies, relative to those predicted    by the independence model (IM).    HMT:  Con-    GTH   centration                    Empirically                              Efficacy       Dosage    Mixing          in Host Soil                    Determined                              Predicted by                                      Efficacy                                             Savings    Ratio  ppm!     Efficacy  the IM  Increment                                              %!    ______________________________________    83:17 6         80        87      -7     -50          3         66        73      -7     -32          2.5       58        54      4      11    50:50 6         78        80      -2     -10          3         65        62      3      8    17:83 6         85        59      26     59          3         44        36      8      21    9:91  6         97        47      50     88          3         42        26      16     42    5:95  6         92        38      56     85          3         36        20      16     47    2:98  6         59        31      28     59    ______________________________________

Example 6 Combinations of 1sodium-1,2,4-triazolate (Na-Tr) anddicyanodiamide (DCD)

The experimental methodology and computerized data analyses employedhere were similar to those employed in the case of Example 1, above.

                  TABLE 8a    ______________________________________    Values of t.sub.50 for Na--Tr alone, DCD alone, and admixtures of the    two.    1-Sodium-1,2,4-Triazolate                  Dicyanodiamide    Concentration Concentration                              Na--Tr:DCD t.sub.50     ppm!          ppm!       Mixing Ratio                                          days!    ______________________________________    0.25                                 9.7    0.5                                  21.4    0.75                                 26.1    1.0                                  31.9    1.5                                  33.7    2.0                                  38.4    5.0                                  41.8                  1.0                    12.4                  2.0                    22.1                  4.0                    26.1                  6.0                    29.6                  10.0                   38.1    5.0           1.0         83:17      52.1    2.5           0.5                    46.7    3.0           3.0         50:50      60.1    1.5           1.5                    51.9    1.0           5.0         17:83      73.2    0.5           2.5                    51.4    0.545         5.445       9:91       64.2    0.273         2.727                  42.9    0.231         5.769       4:96       47.9    0.115         2.885                  35.1    ______________________________________

                  TABLE 8b    ______________________________________    Percentage savings of active ingredients and incremental    improvements in efficacies, relative to those predicted    by the independence model (IM).    Na--Tr:          Con-    DCD   centration                    Empirically                              Efficacy       Dosage    Mixing          in Host Soil                    Determined                              Predicted by                                      Efficacy                                             Savings    Ratio  ppm!     Efficacy  the IM  Increment                                              %!    ______________________________________    83:17 6         78        79      -1     -5          3         70        65      5      20    50:50 6         90        77      13     55          3         78        61      17     51    17:83 6         100       68      32     --          3         77        50      27     66    9:91  6         96        63      33     --          3         64        45      19     53    4:96  6         72        57      15     47          3         53        40      13     41    ______________________________________

Example 7 Combinations of 1-hydro-1,2,4-triazole (Tr) and3-methylpynizole (MP)

The experimental methodology and computerized data analyses employedhere were similar to those employed in the case of Example 1, above.

                  TABLE 9a    ______________________________________    Values of t.sub.50 for Tr alone, MP alone, and admixtures of the two    1-Hydro-1,2,4-Triazole                 3-Methylpyrazole                              Tr:MP     t.sub.50    Concentration  ppm!                 Concentration  ppm!                              Mixing Ratio                                         days!    ______________________________________    0.1                                 5.3    0.25                                14.9    0.5                                 27.8    0.75                                36.8    1.0                                 41.9    1.5                                 48.7    3.0                                 56.9                 0.1                    9.1                 0.25                   24.5                 0.5                    43.6                 0.656                  46.3                 1.0                    48.7                 2.0                    52.3    1.0          1.0          50:50     95.6    0.5          0.5                    72.7    1.818        1.182        91:9      69.8    0.909        0.091                  51.7    1.923        0.077        96:4      59.8    0.962        0.038                  42.8    0.077        1.923         4:96     61.0    0.038        0.962                  52.4    ______________________________________

                                      TABLE 9b    __________________________________________________________________________    Percentage savings of active ingredients and incremental improvements in    efficacies, relative to these predicted by the independence model (IM)          Concentration                 Empirically                        Efficacy    Dosage    Tr:MP in Host Soil                 Determined                        Predicted by                               Efficacy                                    Savings    Mixing Ratio           ppm!  Efficacy                        the IM Increment                                     %!    __________________________________________________________________________    50:50 2      100    90     10   86          1      100    74     26   93    91:9  2      100    83     17   88          1      77     64     13   36    96:4  2      90     81      9   40          1      64     63      1    5     4:96 2      91     88      3   27          1      79     74      5   18    __________________________________________________________________________

Example 8 Combinations of Cu(Tr)₂ !SO₄ ×2H₂ O hydratedcuprotriazole-sulfate complex (CTS) and (GMPH)₂ ZnCl₄1-guanyl-3-methylpyrazoline-chlorozincate complex (GZC)

The experimental methodology and computerized data analyses employedhere were similar to those employed in the case of Example 1, above.

                  TABLE 10a    ______________________________________    Values of t.sub.50 for CTS alone, GZC alone, and admixtures of the two    CTS-Concentration               GZC-Concentration                             CTS:GZC    t.sub.50     ppm!       ppm!         Mixing Ratio                                         days!    ______________________________________    0.1                                 1.9    0.25                                4.9    0.5                                 11.6    1.2                                 27.0    1.8                                 36.1    2.5                                 43.1               0.25                     9.5               0.5                      19.1               0.75                     26.8               1.5                      43.3               3.0                      59.1    1.0        1.0           50:50      77.2    0.5        0.5                      53.6    0.25       0.25                     21.9    1.818      0.182         91:9       45.9    0.909      0.091                    27.8    0.182      1.818          9:91      53.6    0.091      0.909                    30.0    ______________________________________

                                      TABLE 10b    __________________________________________________________________________    Percentage savings of active ingredients and incremental improvements in    efficacies, relative to those predicted by the independence model (IM)          Concentration                 Empirically                        Efficacy    Dosage    CTS:GZC          in Host Soil                 Determined                        Predicted by                               Efficacy                                    Savings    Mixing Ratio           ppm!  Efficacy                        the IM Increment                                     %!    __________________________________________________________________________    50:50 2      100    72     28   84          1      80     42     38   61          0.5    33     19     14   37    91:9  2      69     64      5   14          1      42     36      6   13     9:91 2      80     74      5   16          1      45     51     -5   -15    __________________________________________________________________________

Example 9 Combinations of 1-hydro-1,2,4-triazole (Tr), dicyanodiamide(DCD), and ammonium rhodanide (AR)

The experimental methodology and computerized data analyses employedhere were similar to those employed in the case of Example 1, above.

                                      TABLE 11a    __________________________________________________________________________    Values of t.sub.50 for Tr alone, DCD alone, AR alone, and admixtures of    all three    Tr-Concentration            DCD-Concentration                     AR-Concentration                             Tr:DCD:AR                                    t.sub.50     ppm!    ppm!     ppm!   Mixing Ratio                                     days!    __________________________________________________________________________    0.096                           5.5    0.227                           13.8    0.545                           30.2    0.909                           41.5    1.25                            46.0    2.0                             50.1    3.0                             52.3    5.0                             57.0            1.25                    10.1            2.0                     14.3            3.0                     17.6            3.846                   19.7            5.0                     22.1            5.882                   23.6            8.333                   27.4            10.0                    29.6                     2.0            2.8                     4.0            6.3                     8.0            8.5                     10.0           9.3                     16.0           11.9    0.833   4.167    0.833   14.3:71.4:14.3                                    67.1    0.5     2.5      0.5            52.4    0.385   3.846    0.769    7.7:76.9:15.4                                    58.9    0.231   2.308    0.462          37.7    0.192   3.846    0.962    3.8:77:19.2                                    45.7    0.115   2.308    0.575          34.7    __________________________________________________________________________

                                      TABLE 11b    __________________________________________________________________________    Percentage savings of active ingredients and incremental improvements in    efficacies, relative to those predicted by the independence model (IM)           Concentration                  Empirically                        Efficacy    Dosage    Tr:DCD:AR           in Host Soil                  Determined                        Predicted by                              Efficacy                                    Savings    Mixing Ratio            ppm!  Efficacy                        the IM                              Increment                                     %!    __________________________________________________________________________    14.3:71.4:14.3           5.83   100   67    33    --           3.5    79    53    26    61     7.7:76.9:15.4           5.0    89    53    36    75           3.0    57    39    18    46     3.8:77:19.2           5.0    69    44    25    56           3.0    52    31    21    54    __________________________________________________________________________

Example 10 Combinations of 1-hydro-1,2,4-triazole hydrochloride(Tr×HCl), guanyl thiocarbamide (GTH), and thiocarbamide (TH)

The experimental methodology and computerized data analyses employedhere were similar to those employed in the case of Example 1, above.

                                      TABLE 12a    __________________________________________________________________________    Values of t.sub.50 for Tr × HCl alone, GTH alone, TH alone, and    admixtures of all three    Tr × HCl-             GTH-Concentration                      TH-Concentration                              Tr × HCl:GTH:TH                                       t.sub.50    Concentration  ppm!              ppm!     ppm!   Mixing Ratio                                        days!    __________________________________________________________________________    0.15                               5.0    0.3                                11.5    0.75                               28.4    1.5                                41.3    3.0                                48.9    4.5                                52.1             2.0                       1.9             4.0                       9.5             8.0                       28.1             10.0                      37.0             16.0                      60.1                      2.0              6.3                      4.0              8.7                      8.0              10.9                      10.0             13.0                      16.0             18.1    0.115    2.308    0.577    3.8:77:19.2                                       17.9    0.231    4.615    1.155            44.8    0.115    1.422    1.422    3.8:48.1:48.1                                       11.9    0.231    2.885    2.885            37.9    0.231    1.155    4.615    3.8:19.2:77                                       27.8    0.5      2.0      0.5       17:66:17                                       53.1    0.5      1.25     1.25    16.6:41.7:41.7                                       39.9    0.188    1.875    0.937    6.3:62.5:31.2                                       21.3    0.375    3.75     1.875            47.1    __________________________________________________________________________

                                      TABLE 12b    __________________________________________________________________________    Percentage savings of active ingredients and incremental improvements in    efficacies, relative to those predicted by the independence model (IM)             Concentration                    Empirically                          Efficacy   Dosage    Tr × HCl:GTH:TH             in Host Soil                    Determined                          Predicted by                                Efficacy                                     Savings    Mixing Ratio              ppm!  Efficacy                          the IM                                Increment                                      %!    __________________________________________________________________________     3.8:77:19.2             3.0    27    16    11   36             6.0    67    35    32   57     3.8:48.1:48.1             3.0    19    12     7   28             6.0    57    30    27   51     3.8:19.2:77             6.0    42    25    17   40      17:66:17             3.0    81    33    48   74    16.6:41.7:41.7             3.0    60    30    30   55     6.3:62.5:31.2             3.0    33    17    16   43             6.0    71    38    33   56    __________________________________________________________________________

Example 11 Combinations of 1-guanyl-1,2,4triazole hydrochloride (GTr),dicyanodiamide (DCD), and thiocarbamide (TH)

The experimental methodology and computerized data analyses employedhere were similar to those employed in the case of Example 1, above.

                                      TABLE 13a    __________________________________________________________________________    Values of t.sub.50 for GTr alone, DCD alone, TH alone, and admixtures of    all three    GTr-Concentration             DCD-Concentration                      TH-Concentration                              GTr:DCD:TH                                     t.sub.50     ppm!     ppm!     ppm!   Mixing Ratio                                      days!    __________________________________________________________________________    1.4                              27.5    2.14                             37.5    4.3                              47.3    8.5                              49.2    10.0                             55.2             1.0                     8.9             2.0                     14.2             3.0                     17.1             5.0                     22.3             8.0                     26.8             10.0                    30.1                      2.0            6.3                      4.0            8.7                      8.0            10.9                      10.0           13.0                      16.0           18.1    0.192    3.840    0.968   3.8:76.8:19.4                                     43.8    0.308    6.160    1.54           61.7    0.192    2.404    2.404   3.8:48.1:48.1                                     37.4    0.308    3.846    3.846          57.8    0.192    0.968    3.840   3.8:19.4:76.8                                     27.9    0.308    1.540    6.160          32.7    __________________________________________________________________________

                                      TABLE 13b    __________________________________________________________________________    Percentage savings of active ingredients and incremental improvements in    efficacies, relative to those predicted by the independence model (IM)           Concentration                  Empirically                        Efficacy    Dosage    GTr:DCD:TH           in Host Soil                  Determined                        Predicted by                              Efficacy                                    Savings    Mixing Ratio            ppm!  Efficacy                        the IM                              Increment                                     %!    __________________________________________________________________________    3.8:76.8:19.4           5.0    66    48    18    60           8.0    93    32    61    98    3.8:48.1:48.1           5.0    56    46    10    40           8.0    87    55    31    84    3.8:19.4:76.8           5.0    42    42     0    -1           8.0    49    51    -2    -10    __________________________________________________________________________

Example 12 Combinations of 1-hydro-1,2,4-triazole (Tr), dicyanodiamide(DCD), and ammonium thiosulfate (ATS)

The experimental methodology and computerized data analyses employedhere were similar to those employed in the case of Example 1, above.

                                      TABLE 14a    __________________________________________________________________________    Values of t.sub.50 for Tr alone, DCD alone, ATS alone, and admixtures of    all three    Tr-Concentration            DCD-Concentration                     ATS-Concentration                              Tr:DCD:ATS                                     t.sub.50     ppm!    ppm!     ppm!    Mixing Ratio                                      days!    __________________________________________________________________________    0.096                            5.5    0.227                            14.0    0.545                            30.0    0.909                            41.5    1.25                             46.0    2.0                              50.0    3.0                              52.3    5.0                              57.0            1.25                     10.0            2.0                      14.3            3.0                      17.6            3.846                    19.7            5.0                      22.0            5.882                    23.6            8.333                    27.3            9.091                    28.4            10.0                     29.6                     2.0             0                     4.0             0                     8.0             0                     10.0            0                     16.0            0    0.115   2.308    0.577    4:77:19                                     35.7    0.115   1.422    1.422    4:48:48                                     27.8    0.115   0.577    2.308    4:19:77                                     14.1    __________________________________________________________________________

                                      TABLE 14b    __________________________________________________________________________    Percentage savings of active ingredients and incremental improvements in    efficacies, relative to those predicted by the independence model (IM)           Concentration                  Empirically                        Efficacy    Dosage    Tr:DCD:ATS           in Host Soil                  Determined                        Predicted by                              Efficacy                                    Savings    Mixing Ratio            ppm!  Efficacy                        the IM                              Increment                                     %!    __________________________________________________________________________    4:77:19           3.0    53    35    18    55    4:48:48           3.0    42    30    12    42    4:19:77           3.0    21    24    -3    -20    __________________________________________________________________________

Example 13 Combinations of Fe(Tr)₆ !Cl₃ ferrochlorotriazole complex(Fe--Tr), dicyanodiamide (DCD), and ammonium thiosulfate (ATS)

The experimental methodology and computerized data analyses employedhere were similar to those employed in the case of Example 1, above.

                                      TABLE 15a    __________________________________________________________________________    Values of t.sub.50 for Fe-Tr alone, DCD alone, ATS alone, and admixtures    of all three    Fe-Tr-Concentration             DCD-Concentration                      ATS-Concentration                               Fe-Tr:DCD:ATS                                       t.sub.50     ppm!     ppm!     ppm!    Mixing Ratio                                        days!    __________________________________________________________________________    0.072                              3.9    0.163                              10.3    0.39                               21.2    0.65                               29.4    0.9                                33.3    1.44                               35.7    2.15                               39.4    4.0                                42.9    6.0                                49.9             0.5                       4.8             1.0                       9.3             2.5                       15.4             5.0                       22.6             7.5                       27.3             10.0                      32.8                      2.0              0.09                      4.0              0.09                      6.0              0.1                      8.0              0.1                      10.0             0.1    2.0      2.0      2.0      33.3:33.3:33.3                                       54.6    1.0      1.0      1.0              45.8    0.231    4.615    1.154     3.8:77:19.2                                       51.2    0.115    2.308    0.577            35.8    0.231    2.885    2.885     3.8:48.1:48.1                                       44.9    0.115    1.422    1.422            28.8    0.231    1.154    4.615     3.8:19.2:77                                       29.5    0.115    0.577    2.308            16.7    0.545    4.364    1.091     9.1:72.7:18.2                                       57.9    0.273    2.182    0.545            39.7    __________________________________________________________________________

                                      TABLE 15b    __________________________________________________________________________    Percentage savings of active ingredients and incremental improvements in    efficacies, relative to those predicted by the independence model (IM)            Concentration                   Empirically                         Efficacy   Dosage    Fe-Tr:DCD:ATS            in Host Soil                   Determined                         Predicted by                               Efficacy                                    Savings    Mixing Ratio             ppm!  Efficacy                         the IM                               Increment                                     %!    __________________________________________________________________________    33.3:33.3:33.3            6.0    82    66    16   58            3.0    68    52    16   55     3.8:77:19.2            6.0    77    46    29   76            3.0    53    32    21   63     3.8:48.1:48.1            6.0    67    40    27   69            3.0    43    27    16   56     3.8:19.2:77            6.0    44    32    12   44            3.0    25    21     4   26     9.1:72.7:18.2            6.0    87    55    32   81            3.0    60    39    21   60    __________________________________________________________________________

Example 14 Combinations of Mn(Tr)₄ !Cl₂ manganochlorotriazole complex(MT), Mg(GMP)₂ Cl₂ ×H₂ O hydrated 1-guanyl-3-methyl pyrazolemagnesium-chloride complex (GM), and dicyanodiamide (DCD)

The experimental methodology and computerized data analyses employedhere were similar to those employed in the case of Example 1, above.

                                      TABLE 16a    __________________________________________________________________________    Values of t.sub.50 for MT alone, GM alone, DCD alone, and admixtures of    all three    MT-Concentration             GM-Concentration                      DCD-Concentration                               MT:GM:DCD                                      t.sub.50     ppm!     ppm!     ppm!    Mixing Ratio                                       days!    __________________________________________________________________________    0.2                               5.6    0.5                               15.5    1.0                               28.4    1.5                               35.4    2.0                               42.1    3.0                               49.7             0.2                      8.5             0.6                      25.6             1.0                      42.9             1.5                      46.8             2.0                      48.4                      2.0             20.7                      4.0             25.9                      8.0             31.5                      10.0            35.4                      16.0            52.5    1.667    1.667    1.667    33.3:33.3:33.3                                      106.9    1.0      1.0      1.0             85.7    0.667    0.667    0.667           61.8    0.417    0.417    4.166     8.3:8.3:83.4                                      64.1    0.25     0.25     2.5             44.8    0.167    0.167    1.666           34.1    0.185    0.185    4.630     3.7:3.7:92.6                                      60.7    0.111    0.111    2.778           40.1    0.543    0.109    4.348    10.9:2.1:87                                      54.6    0.109    0.543    4.348     2.1:10.9:87                                      61.4    __________________________________________________________________________

                                      TABLE 16b    __________________________________________________________________________    Percentage savings of active ingredients and incremental improvements in    efficacies, relative to those predicted by the independence model (IM)           Concentration                  Empirically                        Efficacy    Dosage    MT:GM:DCD           in Host Soil                  Determined                        Predicted by                              Efficacy                                    Savings    Mixing Ratio            ppm!  Efficacy                        the IM                              Increment                                     %!    __________________________________________________________________________    33.3:33.3:33.3           5.0    100   89    11    84           3.0    100   76    24    91           2.0    93    62    31    68     8.3:8.3:83.4           5.0    96    64    32    73           3.0    67    45    22    44           2.0    51    31    20    44     3.7:3.7:92.6           5.0    91    54    37    73           3.0    60    37    23    50    10.9:2.1:87           5.0    82    59    23    52     2.1:10.9:87           5.0    92    63    29    67    __________________________________________________________________________

Example 15 Combinations of 1-hydro-1,2,4-triazole (Tr) 3-methylpyrazole(MP), and guanyl thiocarbamide (GTH)

The experimental methodology and computerized data analyses employedhere were similar to those employed in the case of Example 1, above.

                                      TABLE 17a    __________________________________________________________________________    Values of t.sub.50 for Tr alone, MP alone, GTH alone, and admixtures of    all three    Tr-Concentration            MP-Concentration                     GTH-Concentration                              Tr:MP:GTH                                     t.sub.50     ppm!    ppm!     ppm!    Mixing Ratio                                      days!    __________________________________________________________________________    0.1                              5.8    0.25                             14.3    0.5                              29.0    0.75                             42.1    1.0                              49.1    1.5                              51.9    3.0                              56.2            0.1                      9.1            0.25                     24.5            0.5                      43.6            0.656                    46.3            1.0                      48.7            2.0                      52.3                     2.0             1.0                     4.0             9.3                     6.0             18.4                     8.0             28.0                     10.0            37.4                     12.0            47.2    1.667   1.667    1.667    33.3:33.3:33.3                                     112.1    1.0     1.0      1.0             105.7    0.227   0.227    4.546     4.5:4.5:91                                     73.4    0.136   0.136    2.727           47.8    0.119   0.119    4.762     2.4:2.4:95.2                                     44.9    0.071   0.071    2.857           29.3    __________________________________________________________________________

                  TABLE 17b    ______________________________________    Percentage savings of active ingredients and incremental    improvements in efficacies, relative to those predicted    by the independence model (IM).    Tr:MP:          Con-    GTH   centration                    Empirically                              Efficacy       Dosage    Mixing          in Host Soil                    Determined                              Predicted by                                      Efficacy                                             Savings    Ratio  ppm!     Efficacy  the IM  Increment                                              %!    ______________________________________    33.3: 5.0       100       98      2      65    33.3: 3.0       100       92      8      69    33.3    4.5:4.5:          5.0       100       56      44     91    91    3.0       72        35      37     59    2.4:2.4:          5.0       67        40      27     48    95.2  3.0       44        23      21     46    ______________________________________

Example 16 Combinations of 1-hydro-1,2,4-triazole (Tr), 3-methylpyrazole(MP), and dicyanodiamide (DCD)

The experimental methodology and computerized data analyses employedhere were similar to those employed in the case of Example 1, above.

                  TABLE 18a    ______________________________________    Values of t.sub.50 for Tr alone, MP alone, DCD alone,    and admixtures of all three.    Tr-      MP-        DCD-    Concentration             Concentration                        Concentration                                   Tr:MP:DCD                                           t.sub.50     ppm!     ppm!       ppm!      Mixing Ratio                                            days!    ______________________________________    0.1                                    5.2    0.25                                   13.4    0.5                                    28.1    0.75                                   40.7    1.0                                    46.9    1.5                                    49.8    3.0                                    52.1             0.1                           7.6             0.25                          19.4             0.5                           35.7             0.656                         40.1             1.0                           46.1             2.0                           49.7                        0.5                4.1                        1.0                9.1                        2.5                14.2                        5.0                22.3                        10.0               30.7                        13.0               41.8    1.667    1.667      1.667      33.3:33.3:                                           112.9    1.0      1.0        1.0        33.3    102.3    0.227    0.227      4.546      4.5:4.5:91                                           79.4    0.136    0.136      2.727              52.9    0.119    0.119      4.762      2.4:2.4:95.2                                           57.1    0.071    0.071      2.857              41.8    ______________________________________

                  TABLE 18b    ______________________________________    Percentage savings of active ingredients and incremental    improvements in efficacies, relative to those predicted    by the independence model (IM).    Tr:MP:          Con-    DCD   centration                    Empirically                              Efficacy       Dosage    Mixing          in Host Soil                    Determined                              Predicted by                                      Efficacy                                             Savings    Ratio  ppm!     Efficacy  the IM  Increment                                              %!    ______________________________________    33.3: 5.0       100       95      5      82    33.3: 3.0       100       88      12     89    33.3    4.5:4.5:          5.0       100       64      36     94    91    3.0       79        47      32     63    2.4:2.4:          5.0       86        54      32     66    95.2  3.0       63        38      25     54    ______________________________________

We claim:
 1. A method for inhibiting and controlling the nitrificationof ammonium nitrogen in arable soils and substrates, comprising the stepof applying to the soil an amount effective therefor of a compositioncomprising:1 to 35% by weight of a first compound selected from thegroup consisting of 1H-1,2,4-triazole, substituted 1H-1,2,4-triazole andtheir salts, and metallic complexes thereof; 1 to 80% by weight ofdicyanodiamide, 10 to 98% by weight of a third compound selected fromthe group consisting of guanyl thiocarbamide, thiocarbamide, ammoniumrhodanide and ammonium thiosulfate, applied in an amount from 0.2 to 4percent by weight with respect to a nitrogen content of a fertilizercontaining at least one component selected from the group consisting ofammonium and amide.
 2. The method of claim 1 wherein the composition isadministered at a dosage of at least 0.5 kg per hectare.
 3. Incombination,1 to 35% by weight of a first compound selected from thegroup consisting of 1H-1,2,4-triazole, substituted 1H-1,2,4-triazole andtheir salts, and metallic complexes thereof; 1 to 80% by weight ofdicyanodiamide, and 10 to 98% by weight of a third compound which isselected from the group consisting of guanyl thiocarbamide,thiocarbamide, ammonium rhodanide and ammonium thiosulfate, applied inan amount from 0.2 to 4 percent by weight with respect to a nitrogencontent of a fertilizer containing at least one component selected fromthe group consisting of ammonium and amide, for use in inhibiting andcontrolling the nitrification of ammonium nitrogen in arable soils andsubstrates.